CN107326395A - A kind of carbosphere of nickel/N doping is combined the preparation method of hydrogen-precipitating electrode - Google Patents
A kind of carbosphere of nickel/N doping is combined the preparation method of hydrogen-precipitating electrode Download PDFInfo
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- CN107326395A CN107326395A CN201710488063.XA CN201710488063A CN107326395A CN 107326395 A CN107326395 A CN 107326395A CN 201710488063 A CN201710488063 A CN 201710488063A CN 107326395 A CN107326395 A CN 107326395A
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- carbosphere
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 367
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 148
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000006260 foam Substances 0.000 claims abstract description 78
- 238000004070 electrodeposition Methods 0.000 claims abstract description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 30
- 239000008103 glucose Substances 0.000 claims abstract description 29
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 16
- 229930006000 Sucrose Natural products 0.000 claims abstract description 16
- 230000000802 nitrating effect Effects 0.000 claims abstract description 16
- 239000005720 sucrose Substances 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000020477 pH reduction Effects 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 238000007747 plating Methods 0.000 claims description 50
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 239000008367 deionised water Substances 0.000 claims description 41
- 229910021641 deionized water Inorganic materials 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 37
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 36
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 12
- 235000019270 ammonium chloride Nutrition 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 238000011049 filling Methods 0.000 claims description 12
- 239000011174 green composite Substances 0.000 claims description 12
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 12
- DITXJPASYXFQAS-UHFFFAOYSA-N nickel;sulfamic acid Chemical compound [Ni].NS(O)(=O)=O DITXJPASYXFQAS-UHFFFAOYSA-N 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000010935 stainless steel Substances 0.000 claims description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims description 12
- 239000003643 water by type Substances 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- 239000008240 homogeneous mixture Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 35
- 239000001257 hydrogen Substances 0.000 abstract description 35
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000006641 stabilisation Effects 0.000 abstract description 2
- 238000011105 stabilization Methods 0.000 abstract description 2
- 238000002604 ultrasonography Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 60
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 22
- 230000010287 polarization Effects 0.000 description 21
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 11
- 229910052697 platinum Inorganic materials 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 238000012512 characterization method Methods 0.000 description 10
- 230000005611 electricity Effects 0.000 description 10
- 239000012456 homogeneous solution Substances 0.000 description 10
- 150000002171 ethylene diamines Chemical class 0.000 description 9
- -1 polytetrafluoroethylene Polymers 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
A kind of carbosphere of nickel/N doping is combined the preparation method of hydrogen-precipitating electrode, and its key step includes：First using glucose or sucrose as carbon source, ethylenediamine, by adjusting hydrothermal time and the concentration of carbon source, prepares the carbosphere of the nitrating with different size and surface characteristics as nitrogen source；The carbosphere and nickel aminosulfonic bath of nitrating are combined, the carbosphere for preparing nickel/N doping with large surface area and superelevation catalytic activity by the method for easy electro-deposition is combined hydrogen-precipitating electrode；Foam nickel base wherein by ultrasound and acidification is as electro-deposition negative electrode, and three dimensional skeletal structure is that combination electrode improves larger surface area.The carbosphere combination electrode of nickel/N doping prepared by the present invention has unique texture, the catalytic hydrogen evolution performance of big specific surface area and excellent stabilization.
Description
Technical field
The invention belongs to hydrogen producing technology field, more particularly to a kind of preparation method of hydrogen-precipitating electrode.
Technical background
Main energy sources on our times are coal, oil and natural gas, but their reserves are limited, also gradually subtract
It is few, and contain substantial amounts of CO in carbon, sulphur and dust etc., therefore their combustion product because these fuel containx、SOxAnd
NOx, environmental pollution is extremely serious.It recent studies have shown that, the propensity to consume of current Global Oil, collectable oil on the earth
Resource most multipotency was used to 21 century Mo.With the gradually increase and the reduction year by year of reserves of fossil fuel consumption, Yi Jiren
Class increasingly strengthens to the urgency of the regenerative resource of exploitation green, researched and developed to the pay attention to day by day of environmental protection, people
New energy is extremely urgent.
Hydrogen Energy as it is a kind of efficiently, clean and preferable secondary energy sources, received the world since twentieth century seventies
The extensive concern of various countries.As a kind of reproducible secondary energy sources, Hydrogen Energy cleaning, wide source, calorific value height, combustion stability are good,
And can exist with the metal hydride of gaseous state, liquid or solid, adapt to storing and the different requirements of various application environments.
Accessory substance after hydrogen releases energy is water, environmentally friendly, is a kind of preferable energy.However, current more than 90% hydrogen is all
Produced by fossil fuel, this kind of hydrogen production process does not have sustainability, it is impossible to fundamentally solve energy crisis.Electrolysis water
Hydrogen producing technology is a kind of hydrogen production process of sustainable development, is with a wide range of applications.For electrolytic hydrogen production industry, by
In the presence of overpotential of hydrogen evolution, it develops by high energy consumption, the restriction of low energy transformation efficiency, therefore is urged by preparing with height
Change the cathode hydrogen evolution material of activity to reduce overpotential of hydrogen evolution, reduce energy consumption has turned into the key that water electrolysis hydrogen production technology develops.
The electrode material of traditional low overpotential of hydrogen evolution mainly has the noble metals such as Pt, Pd, and these noble metals are stored up on earth
Amount is rare, expensive, it is impossible to realize large-scale promote.Nickel base electrode prepares simple, with low cost, catalysis analysis because it has
The advantages of hydrogen excellent performance and good stability and alkaline medium electrolysis water cathode material for hydrogen evolution is widely used as to drop
Low overpotential of hydrogen evolution, reduces energy consumption, nickel-base alloy electrode and Ni/MoO such as Ni-S, Ni-Mo, Ni-P, Ni-Cox、Ni/
CeO2, the Ni-based combination electrode such as Ni/CNT, Ni/rGO.But, the Hydrogen Evolution Performance of the noble metal such as nickel base electrode and Pt still has very
Big distance, so it is extremely urgent to prepare a kind of nickel-base catalyst of efficient liberation of hydrogen.
The content of the invention
It is an object of the invention to provide a kind of specific surface area that can increase considerably combination electrode, enhancing coating and base
The binding ability at bottom, performance is stable under alkaline environment, nickel/N doping with efficient catalytic Hydrogen Evolution Performance carbosphere is combined
The preparation method of catalytic hydrogen evolution electrode.
The preparation method of the present invention is as follows：
(1) pretreatment of foam nickel base
Foam nickel base is immersed in the container for filling deionized water first, ultrasonically treated 20min；Nickel foam is put into again
Mass ratio is 1:Carry out removing oil processing 20min in 1 ethanol and the mixed solution of acetone；Then nickel foam is immersed into 3M HCl molten
Acidification 30s in liquid, it is therefore an objective to remove the oxide-film of nickel surface；Finally nickel foam is cleaned to neutrality with deionized water, blown
It is dry standby；
(2) hydro-thermal method prepares the carbosphere of N doping
Carbon source is one kind of glucose or sucrose, and nitrogen source is ethylenediamine solution, and 0.5-2g Portugals are added by 10mL deionized waters
The ratio of grape sugar or sucrose, glucose or sucrose is added in deionized water, and be by the volume ratio of ethylenediamine and deionized water
1:300 ratio, adds ethylenediamine, at room temperature magnetic agitation 10min, forms homogeneous mixture solotion, is then transferred into poly-
Tetrafluoroethene inner bag, is sealed in stainless steel autoclave, and the temperature of hydro-thermal reaction is 180 DEG C, and the hydro-thermal reaction time is 4-
10h；Mixed solution is taken out after cooling, and centrifuge washing is carried out with deionized water, until pH=5-7, and dried at 50 DEG C
24h, finally obtains the carbosphere of a diameter of 20nm-3 μm of nitrating；
(3) electro-deposition prepares the carbosphere composite catalyzing electrode of nickel/N doping
Using distilled water as solvent, per liter plating solution 350g containing nickel sulfamic acid, nickel chloride 10g, ammonium chloride 30g and step
(2) prepare N doping carbosphere 0.1-2.0g, bath pH value is 3.5-3.8, by composite plating bath 150W ultrasonic power
Lower processing 2h, obtains homogeneous, blackish green composite plating bath；The composite plating bath prepared is placed in container, electrodeposition process
The middle nickel plate using 2 × 2cm is as anode, and 2 × 2cm nickel foam is as negative electrode, and the spacing of two electrodes is 5cm, during electro-deposition
Between be 60min, electrodeposition temperature be 45 DEG C, electro-deposition current density be 3A/dm2, finally, by the composite deposite of preparation spend from
Sub- water washing and drying, obtain the carbosphere composite catalyzing hydrogen-precipitating electrode of nickel/N doping.
The present invention has the following advantages that compared with prior art：
(1) the nitrating carbosphere surface prepared has a number of oxy radical, with good hydrophily, it is easier to
Disperse in the plating solution；
(2) nitrogen on the carbosphere surface prepared can form activated centre, and place is provided for the crystalline growth of metallic nickel,
Make nano nickel particles dispersed on carbon ball surface, effectively prevent the agglomeration of metallic nickel, what is prepared is Ni-based compound
Electrode has higher surface area and catalytic hydrogen evolution activity；
(3), not only can be with using the three-dimensional porous nickel foam with excellent electric conductivity and corrosion resistance as substrate
Strengthen the binding ability of coating and substrate, performance is stable under alkaline environment；And considerably increase the ratio surface of combination electrode
Product, it is ensured that the gentle body of electrolyte straightway can be passed through；
(5) operate simply, power consumption is few, environmental protection.
Brief description of the drawings
Fig. 1 is the LSV poles of Ni/NC combination electrodes prepared by the embodiment of the present invention 1, embodiment 2, embodiment 3 and embodiment 4
Change curve map；
Fig. 2 is the XRD of Ni/NC combination electrodes prepared by the embodiment of the present invention 3；
Fig. 3 is the TEM figures of the nitrating carbosphere prepared by the embodiment of the present invention 3；
Fig. 4 is the SEM figures of Ni/NC combination electrodes prepared by the embodiment of the present invention 3；
Fig. 5 is Ni/ prepared by the embodiment of the present invention 5, embodiment 6, embodiment 7, embodiment 8, embodiment 9 and embodiment 10
The LSV polarization curves of NC combination electrodes and Ni/NC ' combination electrodes；
Fig. 6 is the TEM figures of the nitrating carbosphere prepared by the embodiment of the present invention 6；
Fig. 7 is the SEM figures of Ni/NC combination electrodes prepared by the embodiment of the present invention 6；
Fig. 8 is the time-measuring electric potential curve map of Ni/NC combination electrodes prepared by the embodiment of the present invention 6.
Embodiment
Embodiment 1
(1) pretreatment of foam nickel base
Foam nickel base is immersed in the beaker for filling deionized water first, ultrasonically treated 20min；Nickel foam is put into again
Ethanol and acetone (VEthanol：VAcetone=1:1) carry out removing oil processing 20min in mixed solution；Then nickel foam is immersed into 3M HCl
Acidification 30s in solution, it is therefore an objective to remove the oxide-film of nickel surface；Finally nickel foam is cleaned to neutrality with deionized water,
Drying is standby.
(2) hydro-thermal method prepares the carbosphere of N doping
3g glucose is weighed with electronic balance and is dissolved in 60mL deionized waters (concentration of glucose is 0.05g/mL), and is added
0.2mL ethylenediamine solutions, magnetic agitation 10min, forms homogeneous solution, is then transferred into 100mL polytetrafluoroethyl-ne at room temperature
In alkene inner bag, it is sealed in stainless steel autoclave, the temperature of hydro-thermal reaction is 180 DEG C, and the hydro-thermal reaction time is 4h.Treat cold
But sample is taken out, sample is subjected to centrifuge washing with deionized water, until pH=5, and 24h is dried at 50 DEG C, finally obtain
The size of the carbosphere of nitrating is about 200nm；
(3) electro-deposition prepares the carbosphere composite catalyzing electrode of nickel/N doping
Using distilled water as solvent, per liter plating solution 350g containing nickel sulfamic acid, nickel chloride 10g, ammonium chloride 30g and step
(2) the carbosphere 0.1g of the N doping prepared, the bath pH value is 3.5, and composite plating bath is located under 150W ultrasonic power
2h is managed, homogeneous, blackish green composite plating bath is obtained.The composite plating bath prepared is placed in beaker, adopted in electrodeposition process
With 2 × 2cm nickel plate as anode, 2 × 2cm nickel foam is as negative electrode, and the spacing of two electrodes is 5cm, and electrodeposition time is
60min, electrodeposition temperature is 45 DEG C, and electro-deposition current density is 3A/dm2.Finally, by the carbon of the nickel/N doping prepared
Microballoon composite deposite is washed with deionized and dried., will be with glucose in order to distinguish the preparation-obtained microballoon of different carbon source
The carbosphere composite catalyzing hydrogen-precipitating electrode of the nickel/N doping prepared for carbon source is named as Ni/NC combination electrodes.
Ni/NC combination electrode performance characterizations：
Using electrochemical workstation, chemical property survey is carried out to the Ni/NC combination electrodes of preparation in three-electrode system
Examination.Working electrode is Ni/NC combination electrodes (1cm2), auxiliary electrode is platinized platinum, and reference electrode is Hg/HgO/ (1M NaOH) electricity
Pole.Using 1M NaOH solutions as electrolyte, LSV polarization curves are tested.As a result as shown in figure 1, being obtained by LSV polarization curves：When
Current density is 10mA/cm2And 100mA/cm2When, the overpotential difference 110mV and 212mV of Ni/NC combination electrode evolving hydrogen reactions.
Embodiment 2
(1) pretreatment of foam nickel base
Foam nickel base is immersed in the beaker for filling deionized water first, ultrasonically treated 20min；Nickel foam is put into again
Ethanol and acetone (VEthanol：VAcetone=1:1) carry out removing oil processing 20min in mixed solution；Then nickel foam is immersed into 3M HCl
Acidification 30s in solution, it is therefore an objective to remove the oxide-film of nickel surface；Finally nickel foam is cleaned to neutrality with deionized water,
Drying is standby.
(2) hydro-thermal method prepares the carbosphere of N doping
9g glucose is weighed with electronic balance and is dissolved in 60mL deionized waters (concentration of glucose is 0.15g/mL), and is added
0.2mL ethylenediamines, magnetic agitation 10min, forms homogeneous solution, is then transferred into 100mL polytetrafluoroethylene (PTFE) at room temperature
In courage, it is sealed in stainless steel autoclave, the temperature of hydro-thermal reaction is 180 DEG C, and the hydro-thermal reaction time is 4h.It is to be cooled to take
Go out sample, sample is subjected to centrifuge washing with deionized water, until pH=6, and 24h is dried at 50 DEG C, finally obtain nitrating
The size of carbosphere be about 200nm；
(3) electro-deposition prepares the carbosphere composite catalyzing electrode of nickel/N doping
Using distilled water as solvent, per liter plating solution 350g containing nickel sulfamic acid, nickel chloride 10g, ammonium chloride 30g and step
(2) the carbosphere 0.5g of the N doping prepared, the bath pH value is 3.6, and composite plating bath is located under 150W ultrasonic power
2h is managed, homogeneous, blackish green composite plating bath is obtained.The composite plating bath prepared is placed in beaker, adopted in electrodeposition process
With 2 × 2cm nickel plate as anode, 2 × 2cm nickel foam is as negative electrode, and the spacing of two electrodes is 5cm, and electrodeposition time is
60min, electrodeposition temperature is 45 DEG C, and electro-deposition current density is 3A/dm2.Finally, by the carbon of the nickel/N doping prepared
Microballoon composite deposite is washed with deionized and dried., will be with glucose in order to distinguish the preparation-obtained microballoon of different carbon source
The carbosphere composite catalyzing hydrogen-precipitating electrode of the nickel/N doping prepared for carbon source is named as Ni/NC combination electrodes.
Ni/NC combination electrode performance characterizations：
Using electrochemical workstation, chemical property survey is carried out to the Ni/NC combination electrodes of preparation in three-electrode system
Examination.Working electrode is Ni/NC combination electrodes (1cm2), auxiliary electrode is platinized platinum, and reference electrode is Hg/HgO/ (1M NaOH) electricity
Pole.Using 1M NaOH solutions as electrolyte, LSV polarization curves are tested.As a result as shown in figure 1, being obtained by LSV polarization curves：When
Current density is 10mA/cm2And 100mA/cm2When, the overpotential difference 98mV and 202mV of Ni/NC combination electrode evolving hydrogen reactions.
Compared with Example 1, with the increase of carbosphere concentration in composite plating bath, the catalytic hydrogen evolution performance of Ni/NC combination electrodes is uprised,
Illustrate, with the increase of carbon ball in composite deposite, the specific surface area of electrode can be increased, so as to improve the avtive spot of evolving hydrogen reaction.
Embodiment 3
(1) pretreatment of foam nickel base
Foam nickel base is immersed in the beaker for filling deionized water first, ultrasonically treated 20min；Nickel foam is put into again
Ethanol and acetone (VEthanol：VAcetone=1:1) carry out removing oil processing 20min in mixed solution；Then nickel foam is immersed into 3M HCl
Acidification 30s in solution, it is therefore an objective to remove the oxide-film of nickel surface；Finally nickel foam is cleaned to neutrality with deionized water,
Drying is standby.
(2) hydro-thermal method prepares the carbosphere of N doping
12g glucose is weighed with electronic balance and is dissolved in 60mL deionized waters (concentration of glucose is 0.2g/mL), and is added
0.2mL ethylenediamines, magnetic agitation 10min, forms homogeneous solution, is then transferred into 100mL polytetrafluoroethylene (PTFE) at room temperature
In courage, it is sealed in stainless steel autoclave, the temperature of hydro-thermal reaction is 180 DEG C, and the hydro-thermal reaction time is 4h.It is to be cooled to take
Go out sample, sample is subjected to centrifuge washing with deionized water, until pH=7, and 24h is dried at 50 DEG C, finally obtain nitrating
The size of carbosphere be about 200nm；
(3) electro-deposition prepares the carbosphere composite catalyzing electrode of nickel/N doping
Using distilled water as solvent, per liter plating solution 350g containing nickel sulfamic acid, nickel chloride 10g, ammonium chloride 30g and step
(2) the carbosphere 1.0g of the N doping prepared, the bath pH value is 3.7, and composite plating bath is located under 150W ultrasonic power
2h is managed, homogeneous, blackish green composite plating bath is obtained.The composite plating bath prepared is placed in beaker, adopted in electrodeposition process
With 2 × 2cm nickel plate as anode, 2 × 2cm nickel foam is as negative electrode, and the spacing of two electrodes is 5cm, and electrodeposition time is
60min, electrodeposition temperature is 45 DEG C, and electro-deposition current density is 3A/dm2.Finally, by the carbon of the nickel/N doping prepared
Microballoon composite deposite is washed with deionized and dried., will be with glucose in order to distinguish the preparation-obtained microballoon of different carbon source
The carbosphere composite catalyzing hydrogen-precipitating electrode of the nickel/N doping prepared for carbon source is named as Ni/NC combination electrodes.
Ni/NC combination electrode performance characterizations：
Using electrochemical workstation, chemical property survey is carried out to the Ni/NC combination electrodes of preparation in three-electrode system
Examination.Working electrode is Ni/NC combination electrodes (1cm2), auxiliary electrode is platinized platinum, and reference electrode is Hg/HgO/ (1M NaOH) electricity
Pole.Using 1M NaOH solutions as electrolyte, LSV polarization curves are tested.As a result as shown in figure 1, being obtained by LSV polarization curves：When
Current density is 10mA/cm2And 100mA/cm2When, the overpotential difference 97mV and 174mV of Ni/NC combination electrode evolving hydrogen reactions.
As shown in Fig. 2 it is observed that (111) (200) (220) three diffraction maximums comply fully with the characteristic peak of metallic nickel, and with
(111) crystal face is preferred orientation.Fig. 3 is, at 180 DEG C, to react 4h, the nitrating that concentration of glucose is prepared when being 0.2g/mL
The transmission electron microscope picture of carbosphere, it can be seen that the size of carbosphere is about 200nm.Fig. 4 is that the Ni/NC prepared is combined
The scanning electron microscope (SEM) photograph of electrode, wherein figure (a) is the scanning figure under small multiplying power, it can be seen that not exposed foam nickel base shows
Reveal and, illustrate that nickel foam is wrapped up by composite catalyst completely in electrodeposition process；Figure (b) is the scanning figure under big multiplying power, can
To find out that nickel particle is smaller, carbosphere surface is densely distributed in, also has some carbospheres to be exposed to coating surface.
Embodiment 4
(1) pretreatment of foam nickel base
Foam nickel base is immersed in the beaker for filling deionized water first, ultrasonically treated 20min；Nickel foam is put into again
Ethanol and acetone (VEthanol：VAcetone=1:1) carry out removing oil processing 20min in mixed solution；Then nickel foam is immersed into 3M HCl
Acidification 30s in solution, it is therefore an objective to remove the oxide-film of nickel surface；Finally nickel foam is cleaned to neutrality with deionized water,
Drying is standby.
(2) hydro-thermal method prepares the carbosphere of N doping
6g glucose is weighed with electronic balance and is dissolved in 60mL deionized waters (concentration of glucose is 0.10g/mL), and is added
0.2mL ethylenediamines, magnetic agitation 10min, forms homogeneous solution, is then transferred into 100mL polytetrafluoroethylene (PTFE) at room temperature
In courage, it is sealed in stainless steel autoclave, the temperature of hydro-thermal reaction is 180 DEG C, and the hydro-thermal reaction time is 4h.It is to be cooled to take
Go out sample, sample is subjected to centrifuge washing with deionized water, until pH=6, and 24h is dried at 50 DEG C, finally obtain nitrating
The size of carbosphere be about 200nm；
(3) electro-deposition prepares the carbosphere composite catalyzing electrode of nickel/N doping
Using distilled water as solvent, per liter plating solution 350g containing nickel sulfamic acid, nickel chloride 10g, ammonium chloride 30g and step
(2) the carbosphere 1.3g of the N doping prepared, the bath pH value is 3.8, and composite plating bath is located under 150W ultrasonic power
2h is managed, homogeneous, blackish green composite plating bath is obtained.The composite plating bath prepared is placed in beaker, adopted in electrodeposition process
With 2 × 2cm nickel plate as anode, 2 × 2cm nickel foam is as negative electrode, and the spacing of two electrodes is 5cm, and electrodeposition time is
60min, electrodeposition temperature is 45 DEG C, and electro-deposition current density is 3A/dm2.Finally, by the carbon of the nickel/N doping prepared
Microballoon composite deposite is washed with deionized and dried., will be with glucose in order to distinguish the preparation-obtained microballoon of different carbon source
The carbosphere composite catalyzing hydrogen-precipitating electrode of the nickel/N doping prepared for carbon source is named as Ni/NC combination electrodes.
Ni/NC combination electrode performance characterizations：
Using electrochemical workstation, chemical property survey is carried out to the Ni/NC combination electrodes of preparation in three-electrode system
Examination.Working electrode is Ni/NC combination electrodes (1cm2), auxiliary electrode is platinized platinum, and reference electrode is Hg/HgO/ (1M NaOH) electricity
Pole.Using 1M NaOH solutions as electrolyte, LSV polarization curves are tested.As a result as shown in figure 1, being obtained by LSV polarization curves：When
Current density is 10mA/cm2And 100mA/cm2When, the overpotential difference 183mV and 313mV of Ni/NC combination electrode evolving hydrogen reactions.
Embodiment 5
(1) pretreatment of foam nickel base
Foam nickel base is immersed in the beaker for filling deionized water first, ultrasonically treated 20min；Nickel foam is put into again
Ethanol and acetone (VEthanol：VAcetone=1:1) carry out removing oil processing 20min in mixed solution；Then nickel foam is immersed into 3M HCl
Acidification 30s in solution, it is therefore an objective to remove the oxide-film of nickel surface；Finally nickel foam is cleaned to neutrality with deionized water,
Drying is standby.
(2) hydro-thermal method prepares the carbosphere of N doping
12g glucose is weighed with electronic balance to be dissolved in 60mL deionized waters (concentration of glucose is 0.20g/mL), and is added
Enter 0.2mL ethylenediamines, at room temperature magnetic agitation 10min, form homogeneous solution, be then transferred into 100mL polytetrafluoroethylene (PTFE)
In inner bag, it is sealed in stainless steel autoclave, the temperature of hydro-thermal reaction is 180 DEG C, and the hydro-thermal reaction time is 10h.Treat cold
But sample is taken out, sample is subjected to centrifuge washing with deionized water, until pH=7, and 24h is dried at 50 DEG C, finally obtain
The size of the carbosphere of nitrating is about 3 μm；
(3) electro-deposition prepares the carbosphere composite catalyzing electrode of nickel/N doping
Using distilled water as solvent, per liter plating solution 350g containing nickel sulfamic acid, nickel chloride 10g, ammonium chloride 30g and step
(2) the carbosphere 0.5g of the N doping prepared, the bath pH value is 3.6, and composite plating bath is located under 150W ultrasonic power
2h is managed, homogeneous, blackish green composite plating bath is obtained.The composite plating bath prepared is placed in beaker, adopted in electrodeposition process
With 2 × 2cm nickel plate as anode, 2 × 2cm nickel foam is as negative electrode, and the spacing of two electrodes is 5cm, and electrodeposition time is
60min, electrodeposition temperature is 45 DEG C, and electro-deposition current density is 3A/dm2.Finally, by the carbon of the nickel/N doping prepared
Microballoon composite deposite is washed with deionized and dried., will be with glucose in order to distinguish the preparation-obtained microballoon of different carbon source
The carbosphere composite catalyzing hydrogen-precipitating electrode of the nickel/N doping prepared for carbon source is named as Ni/NC combination electrodes.
Ni/NC combination electrode performance characterizations：
Using electrochemical workstation, chemical property survey is carried out to the Ni/NC combination electrodes of preparation in three-electrode system
Examination.Working electrode is Ni/NC combination electrodes (1cm2), auxiliary electrode is platinized platinum, and reference electrode is Hg/HgO/ (1M NaOH) electricity
Pole.Using 1M NaOH solutions as electrolyte, LSV polarization curves are tested.As a result as shown in figure 5, being obtained by LSV polarization curves：When
Current density is 10mA/cm2And 100mA/cm2When, the overpotential difference 156mV and 272mV of Ni/NC combination electrode evolving hydrogen reactions.
Embodiment 6
(1) pretreatment of foam nickel base
Foam nickel base is immersed in the beaker for filling deionized water first, ultrasonically treated 20min；Nickel foam is put into again
Ethanol and acetone (VEthanol：VAcetone=1:1) carry out removing oil processing 20min in mixed solution；Then nickel foam is immersed into 3M HCl
Acidification 30s in solution, it is therefore an objective to remove the oxide-film of nickel surface；Finally nickel foam is cleaned to neutrality with deionized water,
Drying is standby.
(2) hydro-thermal method prepares the carbosphere of N doping
12g glucose is weighed with electronic balance to be dissolved in 60mL deionized waters (concentration of glucose is 0.20g/mL), and is added
Enter 0.2mL ethylenediamines, at room temperature magnetic agitation 10min, form homogeneous solution, be then transferred into 100mL polytetrafluoroethylene (PTFE)
In inner bag, it is sealed in stainless steel autoclave, the temperature of hydro-thermal reaction is 180 DEG C, and the hydro-thermal reaction time is 8h.It is to be cooled
Sample is taken out, sample is subjected to centrifuge washing with deionized water, until pH=7, and 24h is dried at 50 DEG C, finally obtain and mix
The size of the carbosphere of nitrogen is about 2 μm；
(3) electro-deposition prepares the carbosphere composite catalyzing electrode of nickel/N doping
Using distilled water as solvent, per liter plating solution 350g containing nickel sulfamic acid, nickel chloride 10g, ammonium chloride 30g and step
(2) the carbosphere 0.5g of the N doping prepared, the bath pH value is 3.6, and composite plating bath is located under 150W ultrasonic power
2h is managed, homogeneous, blackish green composite plating bath is obtained.The composite plating bath prepared is placed in beaker, adopted in electrodeposition process
With 2 × 2cm nickel plate as anode, 2 × 2cm nickel foam is as negative electrode, and the spacing of two electrodes is 5cm, and electrodeposition time is
60min, electrodeposition temperature is 45 DEG C, and electro-deposition current density is 3A/dm2.Finally, by the carbon of the nickel/N doping prepared
Microballoon composite deposite is washed with deionized and dried., will be with glucose in order to distinguish the preparation-obtained microballoon of different carbon source
The carbosphere composite catalyzing hydrogen-precipitating electrode of the nickel/N doping prepared for carbon source is named as Ni/NC combination electrodes.
Ni/NC combination electrode performance characterizations：
Using electrochemical workstation, chemical property survey is carried out to the Ni/NC combination electrodes of preparation in three-electrode system
Examination.Working electrode is Ni/NC combination electrodes (1cm2), auxiliary electrode is platinized platinum, and reference electrode is Hg/HgO/ (1M NaOH) electricity
Pole.Using 1M NaOH solutions as electrolyte, LSV polarization curves are tested.As a result as shown in figure 5, being obtained by LSV polarization curves：When
Current density is 10mA/cm2And 100mA/cm2When, the overpotential difference 134mV and 242mV of Ni/NC combination electrode evolving hydrogen reactions.
Fig. 6 is, at 180 DEG C, to react 8h, the transmission electron microscope picture for the carbosphere of nitrating that concentration of glucose is prepared when being 0.2g/mL,
It can be seen that the size of carbosphere is about 1-2 μm.Fig. 7 is the scanning electron microscope (SEM) photograph of the Ni/NC combination electrodes prepared, its
Middle figure (a) is the scanning figure under small multiplying power, it can be seen that not exposed foam nickel base is displayed, and illustrates electro-deposition
Nickel foam is wrapped up by composite catalyst completely in journey；Figure (b) is the scanning figure under big multiplying power, it can be seen that nickel particle is smaller, is caused
Carbosphere surface is thickly distributed in, also has some carbospheres to be exposed to coating surface.As shown in figure 8, follow current density is
100mA/dm2When, the continued electrolysis time is 72000s, illustrates that Ni/NC combination electrodes prepared by electro-deposition have good stabilization
Property.
Embodiment 7
(1) pretreatment of foam nickel base
Foam nickel base is immersed in the beaker for filling deionized water first, ultrasonically treated 20min；Nickel foam is put into again
Ethanol and acetone (VEthanol：VAcetone=1:1) carry out removing oil processing 20min in mixed solution；Then nickel foam is immersed into 3M HCl
Acidification 30s in solution, it is therefore an objective to remove the oxide-film of nickel surface；Finally nickel foam is cleaned to neutrality with deionized water,
Drying is standby.
(2) hydro-thermal method prepares the carbosphere of N doping
12g glucose is weighed with electronic balance to be dissolved in 60mL deionized waters (concentration of glucose is 0.20g/mL), and is added
Enter 0.2mL ethylenediamines, at room temperature magnetic agitation 10min, form homogeneous solution, be then transferred into 100mL polytetrafluoroethylene (PTFE)
In inner bag, it is sealed in stainless steel autoclave, the temperature of hydro-thermal reaction is 180 DEG C, and the hydro-thermal reaction time is 6h.It is to be cooled
Sample is taken out, sample is subjected to centrifuge washing with deionized water, until pH=5, and 24h is dried at 50 DEG C, finally obtain and mix
The size of the carbosphere of nitrogen is about 500nm；
(3) electro-deposition prepares the carbosphere composite catalyzing electrode of nickel/N doping
Using distilled water as solvent, per liter plating solution 350g containing nickel sulfamic acid, nickel chloride 10g, ammonium chloride 30g and step
(2) the carbosphere 0.5g of the N doping prepared, the bath pH value is 3.6, and composite plating bath is located under 150W ultrasonic power
2h is managed, homogeneous, blackish green composite plating bath is obtained.The composite plating bath prepared is placed in beaker, adopted in electrodeposition process
With 2 × 2cm nickel plate as anode, 2 × 2cm nickel foam is as negative electrode, and the spacing of two electrodes is 5cm, and electrodeposition time is
60min, electrodeposition temperature is 45 DEG C, and electro-deposition current density is 3A/dm2.Finally, by the carbon of the nickel/N doping prepared
Microballoon composite deposite is washed with deionized and dried., will be with glucose in order to distinguish the preparation-obtained microballoon of different carbon source
The carbosphere composite catalyzing hydrogen-precipitating electrode of the nickel/N doping prepared for carbon source is named as Ni/NC combination electrodes.
Ni/NC combination electrode performance characterizations：
Using electrochemical workstation, chemical property survey is carried out to the Ni/NC combination electrodes of preparation in three-electrode system
Examination.Working electrode is Ni/NC combination electrodes (1cm2), auxiliary electrode is platinized platinum, and reference electrode is Hg/HgO/ (1M NaOH) electricity
Pole.Using 1M NaOH solutions as electrolyte, LSV polarization curves are tested.As a result as shown in figure 1, being obtained by LSV polarization curves：When
Current density is 10mA/cm2And 100mA/cm2When, the overpotential difference 149mV and 256mV of Ni/NC combination electrode evolving hydrogen reactions.
Embodiment 8
(1) pretreatment of foam nickel base
Foam nickel base is immersed in the beaker for filling deionized water first, ultrasonically treated 20min；Nickel foam is put into again
Ethanol and acetone (VEthanol：VAcetone=1:1) carry out removing oil processing 20min in mixed solution；Then nickel foam is immersed into 3M HCl
Acidification 30s in solution, it is therefore an objective to remove the oxide-film of nickel surface；Finally nickel foam is cleaned to neutrality with deionized water,
Drying is standby.
(2) hydro-thermal method prepares the carbosphere of N doping
12g sucrose is weighed with electronic balance and is dissolved in 60mL deionized waters (sucrose concentration is 0.20g/mL), and is added
0.2mL ethylenediamines, magnetic agitation 10min, forms homogeneous solution, is then transferred into 100mL polytetrafluoroethylene (PTFE) at room temperature
In courage, it is sealed in stainless steel autoclave, the temperature of hydro-thermal reaction is 180 DEG C, and the hydro-thermal reaction time is 8h.It is to be cooled to take
Go out sample, sample is subjected to centrifuge washing with deionized water, until pH=6, and 24h is dried at 50 DEG C, finally obtain nitrating
The size of carbosphere be about 100nm；
(3) electro-deposition prepares the carbosphere composite catalyzing electrode of nickel/N doping
Using distilled water as solvent, per liter plating solution 350g containing nickel sulfamic acid, nickel chloride 10g, ammonium chloride 30g and step
(2) the carbosphere 2.0g of the N doping prepared, the bath pH value is 3.8, and composite plating bath is located under 150W ultrasonic power
2h is managed, homogeneous, blackish green composite plating bath is obtained.The composite plating bath prepared is placed in beaker, adopted in electrodeposition process
With 2 × 2cm nickel plate as anode, 2 × 2cm nickel foam is as negative electrode, and the spacing of two electrodes is 5cm, and electrodeposition time is
60min, electrodeposition temperature is 45 DEG C, and electro-deposition current density is 3A/dm2.Finally, by the carbon of the nickel/N doping prepared
Microballoon composite deposite is washed with deionized and dried.In order to distinguish the preparation-obtained microballoon of different carbon source, will using sucrose as
The carbosphere composite catalyzing hydrogen-precipitating electrode of nickel/N doping prepared by carbon source is named as Ni/NC ' combination electrodes.
Ni/NC ' combination electrode performance characterizations：
Using electrochemical workstation, chemical property survey is carried out to the Ni/NC ' combination electrodes of preparation in three-electrode system
Examination.Working electrode is Ni/NC ' combination electrodes (1cm2), auxiliary electrode is platinized platinum, and reference electrode is Hg/HgO/ (1M NaOH) electricity
Pole.Using 1M NaOH solutions as electrolyte, LSV polarization curves are tested.As a result as shown in figure 1, being obtained by LSV polarization curves：When
Current density is 10mA/cm2And 100mA/cm2When, Ni/NC ' combination electrode evolving hydrogen reactions overpotential difference 154mV and
309mV。
Embodiment 9
(1) pretreatment of foam nickel base
Foam nickel base is immersed in the beaker for filling deionized water first, ultrasonically treated 20min；Nickel foam is put into again
Ethanol and acetone (VEthanol：VAcetone=1:1) carry out removing oil processing 20min in mixed solution；Then nickel foam is immersed into 3M HCl
Acidification 30s in solution, it is therefore an objective to remove the oxide-film of nickel surface；Finally nickel foam is cleaned to neutrality with deionized water,
Drying is standby.
(2) hydro-thermal method prepares the carbosphere of N doping
3g sucrose is weighed with electronic balance and is dissolved in 60mL deionized waters that (sucrose concentration is 0.05gmL-1), and add
0.2mL ethylenediamines, magnetic agitation 10min, forms homogeneous solution, is then transferred into 100mL polytetrafluoroethylene (PTFE) at room temperature
In courage, it is sealed in stainless steel autoclave, the temperature of hydro-thermal reaction is 180 DEG C, and the hydro-thermal reaction time is 4h.It is to be cooled to take
Go out sample, sample is subjected to centrifuge washing with deionized water, until pH=7, and 24h is dried at 50 DEG C, finally obtain nitrating
The size of carbosphere be about 20nm；
(3) electro-deposition prepares the carbosphere composite catalyzing electrode of nickel/N doping
Using distilled water as solvent, per liter plating solution 350g containing nickel sulfamic acid, nickel chloride 10g, ammonium chloride 30g and step
(2) the carbosphere 0.5g of the N doping prepared, the bath pH value is 3.6, and composite plating bath is located under 150W ultrasonic power
2h is managed, homogeneous, blackish green composite plating bath is obtained.The composite plating bath prepared is placed in beaker, adopted in electrodeposition process
With 2 × 2cm nickel plate as anode, 2 × 2cm nickel foam is as negative electrode, and the spacing of two electrodes is 5cm, and electrodeposition time is
60min, electrodeposition temperature is 45 DEG C, and electro-deposition current density is 3A/dm2.Finally, by the carbon of the nickel/N doping prepared
Microballoon composite deposite is washed with deionized and dried.In order to distinguish the preparation-obtained microballoon of different carbon source, will using sucrose as
The carbosphere composite catalyzing hydrogen-precipitating electrode of nickel/N doping prepared by carbon source is named as Ni/NC ' combination electrodes.
Ni/NC ' combination electrode performance characterizations：
Using electrochemical workstation, chemical property survey is carried out to the Ni/NC ' combination electrodes of preparation in three-electrode system
Examination.Working electrode is Ni/NC ' combination electrodes (1cm2), auxiliary electrode is platinized platinum, and reference electrode is Hg/HgO/ (1M NaOH) electricity
Pole.Using 1M NaOH solutions as electrolyte, LSV polarization curves are tested.As a result as shown in figure 1, being obtained by LSV polarization curves：When
Current density is 10mA/cm2And 100mA/cm2When, Ni/NC ' combination electrode evolving hydrogen reactions overpotential difference 146mV and
286mV。
Embodiment 10
(1) pretreatment of foam nickel base
Foam nickel base is immersed in the beaker for filling deionized water first, ultrasonically treated 20min；Nickel foam is put into again
Ethanol and acetone (VEthanol：VAcetone=1:1) carry out removing oil processing 20min in mixed solution；Then nickel foam is immersed into 3M HCl
Acidification 30s in solution, it is therefore an objective to remove the oxide-film of nickel surface；Finally nickel foam is cleaned to neutrality with deionized water,
Drying is standby.
(2) hydro-thermal method prepares the carbosphere of N doping
12g sucrose is weighed with electronic balance and is dissolved in 60mL deionized waters (sucrose concentration is 0.10g/mL), and is added
0.2mL ethylenediamines, magnetic agitation 10min, forms homogeneous solution, is then transferred into 100mL polytetrafluoroethylene (PTFE) at room temperature
In courage, it is sealed in stainless steel autoclave, the temperature of hydro-thermal reaction is 180 DEG C, and the hydro-thermal reaction time is 10h.It is to be cooled
Sample is taken out, sample is subjected to centrifuge washing with deionized water, until pH=5, and 24h is dried at 50 DEG C, finally obtain and mix
The size of the carbosphere of nitrogen is about 100nm；
(3) electro-deposition prepares the carbosphere composite catalyzing electrode of nickel/N doping
Using distilled water as solvent, per liter plating solution 350g containing nickel sulfamic acid, nickel chloride 10g, ammonium chloride 30g and step
(2) the carbosphere 0.5g of the N doping prepared, the bath pH value is 3.6, and composite plating bath is located under 150W ultrasonic power
2h is managed, homogeneous, blackish green composite plating bath is obtained.The composite plating bath prepared is placed in beaker, adopted in electrodeposition process
With 2 × 2cm nickel plate as anode, 2 × 2cm nickel foam is as negative electrode, and the spacing of two electrodes is 5cm, and electrodeposition time is
60min, electrodeposition temperature is 45 DEG C, and electro-deposition current density is 3A/dm2.Finally, by the carbon of the nickel/N doping prepared
Microballoon composite deposite is washed with deionized and dried.In order to distinguish the preparation-obtained microballoon of different carbon source, will using sucrose as
The carbosphere composite catalyzing hydrogen-precipitating electrode of nickel/N doping prepared by carbon source is named as Ni/NC ' combination electrodes.
Ni/NC ' combination electrode performance characterizations：
Using electrochemical workstation, chemical property survey is carried out to the Ni/NC ' combination electrodes of preparation in three-electrode system
Examination.Working electrode is Ni/NC ' combination electrodes (1cm2), auxiliary electrode is platinized platinum, and reference electrode is Hg/HgO/ (1M NaOH) electricity
Pole.Using 1M NaOH solutions as electrolyte, LSV polarization curves are tested.As a result as shown in figure 1, being obtained by LSV polarization curves：When
Current density is 10mA/cm2And 100mA/cm2When, Ni/NC ' combination electrode evolving hydrogen reactions overpotential difference 225mV and
340mV。
Claims (1)
1. a kind of carbosphere of nickel/N doping with excellent properties is combined the preparation method of hydrogen-precipitating electrode, it is characterised in that：It
Comprise the following steps：
(1) pretreatment of foam nickel base
Foam nickel base is immersed in the container for filling deionized water first, ultrasonically treated 20min；Nickel foam is put into quality again
Than for 1:Carry out removing oil processing 20min in 1 ethanol and the mixed solution of acetone；Then nickel foam is immersed in 3M HCl solutions
Acidification 30s, it is therefore an objective to remove the oxide-film of nickel surface；Finally nickel foam is cleaned to neutrality with deionized water, dried up standby
With；
(2) hydro-thermal method prepares the carbosphere of N doping
Carbon source is one kind of glucose or sucrose, and nitrogen source is ethylenediamine solution, and 0.5-2g glucose is added by 10mL deionized waters
Or the ratio of sucrose, glucose or sucrose are added in deionized water, and be 1 by the volume ratio of ethylenediamine and deionized water:300
Ratio, add ethylenediamine, at room temperature magnetic agitation 10min, formed homogeneous mixture solotion, be then transferred into polytetrafluoroethyl-ne
Alkene inner bag, is sealed in stainless steel autoclave, and the temperature of hydro-thermal reaction is 180 DEG C, and the hydro-thermal reaction time is 4-10h；Treat
Mixed solution is taken out after cooling, centrifuge washing is carried out with deionized water, until pH=5-7, and 24h is dried at 50 DEG C, finally
Obtain the carbosphere of a diameter of 20nm-3 μm of nitrating；
(3) electro-deposition prepares the carbosphere composite catalyzing electrode of nickel/N doping
Using distilled water as solvent, per liter plating solution 350g containing nickel sulfamic acid, nickel chloride 10g, ammonium chloride 30g and step (2)
The carbosphere 0.1-2.0g of the N doping of preparation, bath pH value is 3.5-3.8, and composite plating bath is located under 150W ultrasonic power
2h is managed, homogeneous, blackish green composite plating bath is obtained；The composite plating bath prepared is placed in container, adopted in electrodeposition process
With 2 × 2cm nickel plate as anode, 2 × 2cm nickel foam is as negative electrode, and the spacing of two electrodes is 5cm, and electrodeposition time is
60min, electrodeposition temperature is 45 DEG C, and electro-deposition current density is 3A/dm2, finally, by the composite deposite deionized water of preparation
Wash and dry, obtain the carbosphere composite catalyzing hydrogen-precipitating electrode of nickel/N doping.
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| CN108998809A (en) * | 2018-08-03 | 2018-12-14 | 武汉工程大学 | A kind of electrode catalytic materials and its preparation method and application of double layer nickel array structure |
| CN110735152A (en) * | 2019-10-25 | 2020-01-31 | 燕山大学 | Ni-Cu-C electrocatalyst, and preparation method and application thereof |
| CN111013621A (en) * | 2019-11-14 | 2020-04-17 | 河南城建学院 | Method for producing transition metal carbonitrides |
| CN113755883A (en) * | 2021-07-22 | 2021-12-07 | 齐齐哈尔大学 | Preparation method and performance of biomass boron-doped carbon sphere induced manganese oxide composite catalyst electrode |
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Cited By (5)
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| CN108998809A (en) * | 2018-08-03 | 2018-12-14 | 武汉工程大学 | A kind of electrode catalytic materials and its preparation method and application of double layer nickel array structure |
| CN108998809B (en) * | 2018-08-03 | 2020-04-17 | 武汉工程大学 | Electrode catalytic material with double-layer nickel array structure and preparation method and application thereof |
| CN110735152A (en) * | 2019-10-25 | 2020-01-31 | 燕山大学 | Ni-Cu-C electrocatalyst, and preparation method and application thereof |
| CN111013621A (en) * | 2019-11-14 | 2020-04-17 | 河南城建学院 | Method for producing transition metal carbonitrides |
| CN113755883A (en) * | 2021-07-22 | 2021-12-07 | 齐齐哈尔大学 | Preparation method and performance of biomass boron-doped carbon sphere induced manganese oxide composite catalyst electrode |
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Denomination of invention: Preparation method of nickel/nitrogen doped carbon microsphere composite hydrogen evolution electrode Effective date of registration: 20231026 Granted publication date: 20190222 Pledgee: Changle Shandong rural commercial bank Limited by Share Ltd. Pledgor: Shandong Haihe Energy Technology Co.,Ltd. Registration number: Y2023980062853 |